Non-opaque flame retardant polycarbonate composition

ABSTRACT

A non-opaque flame retardant polycarbonate composition comprising in admixture an aromatic carbonate polymer and a flame retardant additive which may be the metal salts of either monomeric or polymeric substituted aromatic sulfonic acids, or mixtures thereof; said aromatic carbonate polymer and additive having a refractive index in the range of 1.54 to 1.65.

This application is a continuation-in-part of Patent Application Ser.No. 429,120, filed Dec. 28, 1973, now U.S. Pat. No. 3,940,366 issuedFeb. 24, 1976.

This invention is directed to a non-opaque flame retardant polycarbonatecomposition and in particular an aromatic polycarbonate containing inadmixture therewith an additive which may be the metal salts of eithermonomeric or polymeric aromatic sulfonic acids, or mixtures thereofwherein said aromatic polycarbonate and additive have a refractive indexin the range of 1.54 to 1.65 and articles therefrom.

BACKGROUND OF THE INVENTION

With the increasing concern for safety, there is a positive move towardsproviding safe materials for public and household use. One particulararea of need is that of providing flame resistant or flame retanrantnon-opaque products for use by the ultimate consumer. As a result ofthis demand, many non-opaque products are being required to meet certainflame retardant criteria both by local and federal government and themanufacturers of such products. One particular set of conditionsemployed as a measuring standard for flame retardancy is set forth inUnderwriters' Laboratories, Inc. Bulletin 94. This Bulletin sets forthcertain conditions by which materials are rated for self-extinguishingcharacteristics.

In the art, there are many known flame retardant additives which areemployed by mixing with products to render such materialsself-extinguishing or flame retardant. Such flame retardant additiveshave been known to be employed in amounts of 5 to 20 weight percent inorder to be effective in extinguishing burning of those products whichare combustible. It has also been found that such amounts can have adegrading effect upon the base product to be rendered flame retardant,resulting in the losses of valuable physical properties of the baseproduct as well as rendering the product opaque. This is particularly sowhen employing known flame retardant additives with the base productpolycarbonate resins. Many of these known additives have a degradingeffect upon the polymer.

In many instances, it is desirable that articles produced from thesefire retarded polycarbonate resins retain their non-opaquecharacteristics.

DESCRIPTION OF THE INVENTION

It has now been surprisingly discovered that an aromatic polycarbonatecan be made flame retardant while retaining its non-opaquecharacteristics by incorporating with the aromatic polycarbonate from0.001 to about 2.0 parts per hundred parts of aromatic polycarbonate ofcertain additives, which additives are inert and do not degrade thearomatic polycarbonate.

The shaped artilce of the present invention is that comprising anaromatic carbonate polymer and from 0.001 to about 2.0 parts per hundredparts of aromatic carbonate polymer of an additive selected from thegroup consisting of a metal salt of a monomeric substituted aromaticsulfonic acid and a polymeric substituted sulfonic acid or mixturesthereof, and wherein said metal salts thereof are selected from thegroup consisting of the alkali metal salts and the alkaline earth metalsalts, and mixtures thereof, and said substituent on the metal salts ofthe substituted aromatic sulfonic acid is selected from the groupconsisting of an electron withdrawing radical and mixtures thereofwherein the shaped article has a refractive index in the range of 1.54to 1.65. Preferably, shaped articles are in the form of a sheet and apellet.

The refractive indicies of the materials herein are determined by theimmersion method as described in Physical Methods of Organic Chemistry,by Arnold Weissberger, Interscience Publishers, Volumn II, 1960 (page1433).

When the refractive index of the instant additives is in the range ofthe refractive index of the aromatic carbonate polymer, i.e., 1.54 to1.65, the polycarbonate composition and shaped article producedtherefrom is nonopaque. This means that it is able to transmit light andis from transclucent to transparent. Depending upon how close therefractive index of the additive is to that of the polycarbonate, thiswill determine whether the resulting composition is transparent ortranslucent. If the additive at the concentration employed is partiallyor totally soluble in the polycarbonate polymer, the more transparentthe composition and resulting article will be.

More specifically, the particular additive of this invention is themetal salt of either the monomeric or polymeric substituted aromaticsulfonic acid or mixtures thereof having a refractive index in the rangeof 1.54 to 1.65. The metal salt employed in the practice of thisinvention is either the alkali metal or alkaline earth metal salt andmixtures thereof. The metals of these groups are sodium, lithium,potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium,and barium.

The aromatic sulfonic acid employed in the practice of this invention isa substituted aromatic sulfonic acid wherein the substituent consists ofan electron withdrawing radical. As employed herein and within the scopeof this invention, any of the electron withdrawing radicals can beemployed in the practice of this invention. However, preferably, theelectron withdrawing radical or substituent employed in the practice ofthis invention is the halo-, nitro-, trihalomethyl and cyano electronwithdrawing radicals or mixtures of these electron withdrawing radicals.

The electron withdrawing phenomenon, or as it is also referred to aselectronegativity, is defined in Basic Principles of Organic Chemistryby Roberts and Caserio, 1964 (pages 185-186), and Physical OrganicChemistry by Jack Hine, McGraw-Hill Book Company, Inc. 1962 (pages 5, 32and 85-93). Briefly, the electron withdrawing phenomenon is where theradical has a strong affinity for a negative charge, namely electrons,but still remains covalent and does not form an ion. This is anextremely brief description of this phenomenon and is merely set forthhere to describe the electron withdrawing effect. Reference should bemade to the texts set forth above.

In the practice of this invention, the types of sulfonic acids employedherein may be either the monomeric form or the polymeric form ormixtures of these. When first considering the monomeric form, the metalsalt of the substituted monomeric aromatic sulfonic acid can best berepresented by the following formula:

    [A].sub.0-1 [R].sub.0-1 [B]                                I.

wherein [A] and [B] can, in turn be independently selected from thefollowing formula:

    R'.sub.x (SO.sub.3 M).sub.y R"                             II

    r'.sub.x (SO.sub.3 M).sub.y R"                             II

wherein R' is an electron withdrawing radical, M is a metal which may beselected from the periodic table of either an alkali metal or analkaline earth metal, R" is an aryl radical of 1-4 aromatic rings, x isan integer of 014 17 and y an integer of 0-10. It is to be understood,however, that x in Formula II must equal at least 1 and y in Formula IImust equal at least 1.

In Formula I above, [R] is an organic radical of 1-20 carbon atoms andis either alkyl, aralkyl, alkenyl, aralkenyl, aryl, arylene, alkylene,aralkylene, alkenylene, aralkenylene, alkylidene, aralkylidene,alkenylidene or aralkenylidene. It should also be understood that theradical [R] can also contain halogen substituents which would be anelectron withdrawing radical. However, this would be in addition to theabove requirement that in Formula I the sum of x must be at least 1.

In the above Formula I, the combination of the electron withdrawingradical and the (SO₃ M) radical is the novel feature of the instantinvention that offers the excellent flame retardant properties whenadmixed with an aromatic polycarbonate. Preferably, for optimum results,the electron withdrawing radical and the (SO₃ M) radical should be onthe same aromatic ring, namely either in [A] or [B] of Formula I above.As further indicated above in Formula I in its simplest form, the flameretardant additive can consist merely of [B] which in turn would besimply Formula II. This is shown where [A] and [R] may be zero (0).

Obviously, the simplest formula may be as follows: ##STR1## and morespecifically ##STR2##

Actually, while there are many compounds that meet the requirements ofFormula I and which offer excellent flame retardant characteristics toan aromatic polycarbonate, the preferred additive employed in themonomeric form is the sodium salt of 2,4,5-trichlorobenzenesulfonicacid. This has the following formula: ##STR3## Mixtures of the variousmetal salts of the monomeric substituted sulfonic acids can be employedherein.

When the polymeric form of the substituted aromatic sulfonic acid isemployed in the practice of this invention, it can best be representedby the following formula:

    [A].sub.m [R].sub.m+n [B].sub.n                            III.

wherein [A] and [B] are independently selected from the followingformula:

    R'.sub.x (SO.sub.3 M).sub.y R"                             IV.

wherein R', M, R", x and y have the same meaning as recited previously.In addition, the same requirements for x and y also apply. However, itis also understood that [A] and [B] units can be randomly selected. Inaddition, [R₁ ] is an organic radical of 1-20 carbon atoms and is eitherarylene, alkylene, aralkylene, alkenylene, aralkenylene, alkylidene,aralkylidene, alkenylidene and aralkenylidene. In the polymeric form,[R₁ ] cannot be monovalent as in the case of monomeric form of theadditive employed herein and described by Formula I. In Formula III, thesum of m and n must be at least 4 and can be as high as 2000. As shown,the selection of m and n can be random or equal or one can be 0. InFormula III, R₁ can also contain halogen substituents which would be anelectron withdrawing radical. However, this would be in addition to therequirement that in Formula III, the sum of x must be at least 1.

In the practice of this invention, it is to be understood that thepolymeric structure can be either a homopolymer, a copolymer, a randomcopolymer, a block copolymer or a random block copolymer includingmixtures thereof. In addition, the ratio of sulfonated aromatic rings tounsulfonated aromatic rings can vary from greater than 1 to 1 to as highas that which is barely necessary to render the polycarbonate flameretardant and this may be 1 to 100.

The compositions of the instant invention may contain fillers, pigments,dyes, antioxidants, stabilizers, ultraviolet light absorbers, moldrelease agents and other additives commonly employed in non-opaquepolycarbonate resin formulations. Furthermore, the shaped articles maybe coated with, for example, mar or scratch-resistant coatings.

PREFERRED EMBODIMENT OF THE INVENTION

In order to more fully and clearly illustrate the present invention, thefollowing specific examples are presented. It is intended that theexamples be considered as illustrative rather than limiting theinvention disclosed and claimed herein. In the examples, all parts andpercentages are on a weight basis unless otherwise specified.

EXAMPLE I

One hundred parts of an aromatic polycarbonate, prepared by reacting2,2-bis(4-hydroxyphenyl) propane and phosgene in the presence of an acidacceptor and a molecular weight regulator and having an intrinsicviscosity of 0.57 is mixed with 0.05 part of a finely ground dehydratedadditive listed in Table I by tumbling the ingredients together in alaboratory tumbler. The resulting mixture is then fed to an extruder,which extruder is operated at about 265° C, and the extrudate iscomminuted into pellets.

The pellets are then injection molded at about 315° C into test bars ofabout 5 in. by 1/2 in. by about 1/16 -1/8 in. thick into test squares ofabout 2 in. by 2 in. by about 1/8 in. thick. The test bars (5 for eachadditive listed in the Table) are subject to the test procedure setforth in Underwriters' Laboratories, Inc. Bulletin UL-94, Burning Testfor Classifying Materials. In accordance with this test procedure,materials so investigated are rated either V-0, V-I or V-II based on theresults of 5 specimens. The criteria for each V (for vertical) ratingper UL-94 is briefly as follows:

"V-O": Average flaming and/or glowing after removal of the ignitingflame shall not exceed 5 seconds and none of the specimens shall dripflaming particles which ignite absorbent cotton.

"V-I": Average flaming and/or glowing after removal of the ignitingflame shall not exceed 25 seconds and the glowing does not travelvertically for more than 1/8 inch of the specimen after flaming ceasesand glowing is incapable of igniting absorbent cotton.

"V-II": Average flaming and/or glowing after removal of the ignitingflame shall not exceed 25 seconds and the specimens drip flamingparticles which ignite absorbent cotton.

In addition, a test bar which continues to burn for more than 25 secondsafter removal of the igniting flame is classified, not by UL-94, but bythe standards of the instant invention, as "burns". Further, UL-94requires that all test bars in each test group must meet the V typerating to achieve the particular classification. Otherwise, the 5 barsreceive the rating of the worst single bar. For example, if one bar isclassified as V-II and the other four (4) are classified as V-0, thenthe rating for all 5 bars is V-II.

The test squares are tested for light transmission in a Gardner XL10-CDM instrument. The data shows the amount of incident lighttransmitted by the test squares using air as 100% transmission.

The result of an additive within the scope of the instant invention isas follows with a control being the aromatic polycarbonate as preparedabove without the additive of the type set forth herein.

                  TABLE 1                                                         ______________________________________                                                                       No. of                                                       Light   Flame    Drips                                                        Trans-  Out      Per                                            Additive      mission Time     five   UL-94                                   (0.05 parts per hundred)                                                                    (%)     Seconds  test bars                                                                            Rating                                  ______________________________________                                        CONTROL       89      24       13     Burning                                 Sodium                                                                        2,4,5-trichloro benzene                                                       sulfonate     87      9.8       0     V-I                                     ______________________________________                                    

EXAMPLE II

This Example is set forth to demonstrate the effect of the additives ofthis invention at limits of 0.30 parts per hundred parts of thepolycarbonate.

In preparing the test specimen for this Example, 100.00 parts of thepolycarbonate of Example I is mixed with 0.06 parts of the additivelisted in Table 2 employing the same procedure. Test specimens are thenmolded using the same procedure employed in Example I. The testspecimens are subjected to the same test procedure of Example I with thefollowing results:

                  TABLE 2                                                         ______________________________________                                                                       No. of                                                       Light   Flame    Drips                                                        Trans-  Out      Per                                            Additive      mission Time     five   UL-94                                   (0.06 parts per hundred)                                                                    (%)     Seconds  test bars                                                                            Rating                                  ______________________________________                                        CONTROL       89      24       13     Burning                                 Sodium                                                                        2,4,5-trichloro benzene                                                       sulfonate     76      3.2       0     V-O                                     ______________________________________                                    

EXAMPLE III

This Example is set forth to demonstrate the effect of the additives ofthis invention at limits of 0.10 parts per hundred parts of thepolycarbonate.

In preparing the test specimens for this Example, 100.00 parts of thepolycarbonate of Example I is mixed with 0.10 parts of the additiveslisted in Table 3 employing the same procedure. Test specimens are thenmolded using the same procedure employed in Example I. The testspecimens are subjected to the same test procedure of Example I with thefollowing results:

                  TABLE 3                                                         ______________________________________                                                                       No. of                                                       Light   Flame    Drips                                                        Trans-  Out      Per                                            Additive      mission Time     five   UL-94                                   (0.10 parts per hundred)                                                                    (%)     Seconds  test bars                                                                            Rating                                  ______________________________________                                        CONTROL       89      24       13     Burning                                 Sodium                                                                        2,4,5-trichloro benzene                                                       sulfonate     76      3.2      0      V-O                                     Potassium                                                                     2,4,5-trichlorobenzene                                                        sulfonate     66      2.5      0      V-O                                     Sodium 1,1-                                                                   bis(4-chlorophenyl)-2-                                                        chloroethylene-3-                                                                           83      2.3      0      V-O                                     sulfonate                                                                     ______________________________________                                    

EXAMPLE IV

This Example is set forth to demonstrate the effect of the additives ofthis invention at limits of 0.50 parts per hundred parts of thepolycarbonate.

In preparing the test specimens for this Example, 100.00 parts of thepolycarbonate of Example I is mixed with 0.50 parts of the additiveslisted in Table 4 employing the same procedure. Test specimens are thenmolded using the same procedure employed in Example I. The testspecimens are subjected to the same test procedure of Example I with thefollowing results:

                  TABLE 4                                                         ______________________________________                                                                       No. of                                                       Light   Flame    Drips                                                        Trans-  Out      Per                                            Additive      mission Time     five   UL-94                                   (0.50 parts per hundred)                                                                    (%)     Seconds  test bars                                                                            Rating                                  ______________________________________                                        CONTROL       89      24       13     Burning                                 Sodium trichloro-                                                             biphenyl sulfonate                                                                          83      4.0      0      V-O                                     Sodium heptachloro-                                                           biphenyl sulfonate                                                                          84      2.0      0      V-O                                     Sodium 1,1-                                                                   bis(4-chlorophenyl)-2,2-                                                      dichloroethylene-3-                                                                         69      2.7      0      V-O                                     sulfonate                                                                     Sodium 1,1-                                                                   bis(4-chlorophenyl)-1-                                                        chloroethylene-3-                                                                           83      2.3      0      V-O                                     sulfonate                                                                     ______________________________________                                    

EXAMPLE V

This example is set forth to demonstrate the effect of the additives ofthis invention at limits of 1.0 parts per hundred parts of thepolycarbonate.

In preparing the test specimens for this Example, 100.00 parts of thepolycarbonate of Example I is mixed with 1.0 parts of the additiveslisted in Table 5 employing the same procedure. Thest specimens are thenmolded using the same procedure employed in Example I. The testspecimens are subjected to the same test procedure of Example I with thefollowing results:

                  TABLE 5                                                         ______________________________________                                                                       No. of                                                       Light   Flame    Drips                                                        Trans-  Out      Per                                            Additive      mission Time     five   UL-94                                   (1.0 parts per hundred)                                                                     (%)     Seconds  test bars                                                                            Rating                                  ______________________________________                                        CONTROL       89      24       13     Burning                                 Sodium 2,5-dichloro-                                                          benzene sulfonate                                                                           71      1.9      0      V-O                                     Disodium 2,5-                                                                 dichlorobenzene-1,3-                                                          disulfonate   68      2.4      0      V-O                                     Sodium 2-chloro-5-                                                            bromobenzene sulfonate                                                                      63      2.8      0      V-O                                     Sodium 2-chloro-4-                                                            bromobenzene sulfonate                                                                      64      2.1      0      V-O                                     Calcium 3,4,5-trichloro-                                                      benzene sulfonate                                                                           61      2.4      0      V-O                                     Barium 2,4,5-trichloro-                                                       benzene sulfonate                                                                           63      3.8      0      V-O                                     Sodium trichloro-                                                             biphenyl sulfonate                                                                          81      2.6      0      V-O                                     Sodium heptachloro-                                                           biphenyl sulfonate                                                                          82      2.3      0      V-O                                     ______________________________________                                    

EXAMPLE V

This Example is set forth to show the effect of a known commerciallyavailable flame retardant additive.

Example I is repeated except that in place of the additives employedtherein, only 1 part decabromodiphenyl ether is used herein. The resultsobtained upon evaluating 5 test bars are the same as obtained for theControl shown in Table 1 above.

In the practice of this invention, aromatic carbonate polymers arerendered flame retardant by the addition of certain particular additiveswhich are the metal salts of substituted and unsubstituted monomeric orpolymeric aromatic sulfonesulfonates and include mixtures of these. Theamount of the additives employed in the practice of this invention mayvary from 0.001 to up to about 2.0 parts per hundred parts of aromaticpolycarbonate.

As indicated previously, the additive of the instant invention comprisesthe alkali or alkaline earth metal salts of the monomeric or polymericaromatic sulfonic acids or mixtures thereof having a refractive index inthe range of 1.54 to 1.65. While a great number of such salts are setforth in the tables of the Examples of the instant invention, these areonly a representative sample of the additives of this invention. Thesodium, calcium, magnesium, potassium, strontium, lithium, barium,rubidium and cesium salts of other aromatic sulfonic acids can beemployed in place of those of the Examples with the same effective flameretardancy being achieved. These other aromatic sulfonic acids are

p-fluorobenzene sulfonic acid

2,3,4,5-tetrafluorobenzenesulfonic acid

pentafluorobenzenesulfonic acid

p-chlorobenzenesulfonic acid

2,4-dichlorobenzenesulfonic acid

p-bromobenzenesulfonic acid

2,5-dibromobenzenesulfonic acid

2-bromo-4-chlorobenzenesulfonic acid

2-chloro-4-bromobenzenesulfonic acid

2-bromo-5-chlorobenzenesulfonic acid

2-chloro-5-bromobenzenesulfonic acid

2,3,4-trichlorobenzenesulfonic acid

2,4,6-trichlorobenzenesulfonic acid

2,3,4,5-tetrachlorobenzenesulfonic acid

2,3,5,6-tetrachlorobenzenesulfonic acid

2,3,4,6-tetrachlorobenzenesulfonic acid

pentachlorobenzenesulfonic acid

1-chloronaphthalene-x-sulfonic acid 1,x-dichloronaphthalene-y-sulfonicacid

1-bromonaphthalene-x-sulfonic acid

4,5-dichlorobenzene-1,3-disulfonic acid

In the practice of this invention, the additive is generally prepared bywell known methods in the art. For example, one such well known methodinvolves taking an aromatic hydrocarbon such as benzene and contactingit with either of the electron withdrawing components such as throughchlorination, bromination or nitration. This is then subjected tosulfonation using either sulfuric acid, chlorosulfonic acid, fumingsulfuric acid or sulfur trioxide. These reactions can be carried out atroom temperature or at elevated temperatures such as about 50° C.Alternatively, the order of the above reaction can be reversed. The saltis then prepared by adding the proper alkaline reagent in sufficientamount to make the neutral salt. The salt is then recovered byprecipitation or by distillation of the solvent.

In the case of the trihalomethyl electron withdrawing substituent, suchas trifluoromethyl electron withdrawing substituent, it is best to startwith the prepared trifluoromethyl aromatic hydrocarbon and thensulfonate as above, as well as preparing the salt thereof.

In the case of the cyano-substituent, it is best to prepare the sulfonicacid by oxidation of the corresponding thiophenol by hydrogen peroxideor or organic peracide. The salt is then made as above and recoveredaccordingly. This technique is also best for the preparation of sulfonicacids with the trichloromethyl substituent.

In the practice of this invention, any of the aromatic polycarbonatescan be employed herein having a refractive index in the rante of 1.54 to1.65. These are homopolymers and copolymers and mixtures thereof thatare prepared by reacting a dihydric phenol with a carbonate precursor.Typical of some of the dihydric phenols that may be employed in thepractice of this invention are bisphenol-A, (2,2-bis(4-hydroxyphenyl)propane), bis(4-hydroxyphenyl) methan, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4-bis(4-hydroxyphenyl) heptane,2,2-(3,5,3',5'-tetrachloro-4,4'-dihydroxydiphenyl) propane,2,2-(3,5,3',5'-tetrabromo-4,4'-dihydroxydiphenyl) propane,(3,3'-dichloro-4,4'-dihydroxyphenyl) methane. Other dihydric phenols ofthe bisphenol type are also available and are disclosed in U.S. Pat.Nos. 2,999,835, 3,028,365 and 3,334,154.

It is, of course, possible to employ two or more different dihydricphenols or a copolymer of a dihydric phenol with a glycol or withhydroxy or acid terminated polyester, or with a dibasic acid in theevent a carbonate copolymer or interpolymer rather than a homopolymer isdesired for use in the preparation of the aromatic carbonate polymers ofthis invention. Also, employed in the practice of this invention may beblends of any of the above materials to provide the aromatic carbonatepolymer.

The carbonate precursor may be either a carbonyl halide, a carbonateester or a haloformate. The carbonyl halides which can be employedherein are carbonyl bromide, carbonyl chloride and mixtures thereof.Typical of the carbonate esters which may be employed herein arediphenyl carbonate, di(halophenyl) carbonates such as di-(chloropheyl)carbonate, di-(bromophenyl) carbonate, di-(trichlorophenyl) carbonate,di-(tribromophenyl) carbonate, etc., di-(alkylphenyl) carbonate such asdi(tolyl) carbonate, etc., di-(naphthyl) carbonate, di-(chloronaphthyl)carbonate, phenyl tolyl carbonate, chlorophenyl chloronaphthylcarbonate, etc., or mixtures thereof. The haloformates suitable for useherein include bis-holoformates of dihydric phenols (bischloroformatesof hydroquinone, etc.) or glycols (bishaloformates of ethylene glycol,neopentyl glycol, polyethylene glycol, etc.). While other carbonateprecursors will occur to those skilled in the art, carbonyl chloridealso known as phosgene is preferred.

Also included are the polymeric derivatives of a dihydric phenol, adicarboxylic acid and carbonic acid. These are disclosed in U.S. Pat.No. 3,169,121 which is incorporated herein by reference.

The aromatic charbonate polymers of this invention may be prepared byemploying a molecular weight regulator, an acid acceptor and a catalyst.The molecular weight regulators which can be employed in carrying outthe process of this invention include monohydric phenols such as phenol,chroman-I, paratertiary-butylphenol, papabromophenol, primary andsecondary amines, etc. Preferably, phenol is employed as the molecularweight regulator.

A suitable acid acceptor may be either an organic or an inorganic acidacceptor. A suitable organic acid acceptor is a tertiary amine andincludes such materials as pyridine, triethylamine, dimethylaniline,tributylamine, etc. The inorganic acid acceptor may be one which can beeither a hydroxide, a carbonate, a bicarbonate, or a phosphate of analkali or alkaline earth metal.

The catalysts which are employed herein can be any of the suitablecatalysts that aid the polymerization of bisphenol-A with phosgene.Suitable catalysts include tertiary amines such as for example,triethylamine, tripropylamine, N,N-dimethylaniline, quaternary ammoniumcompounds such as for example tetraethylammonium bromide, cetyl triethylammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propylammoniumbromide, tetramethylammonium chloride, tetramethyl ammonium hydroxide,tetra-n-butylammonium iodide, benzyltrimethylammonium chloride andquaternary phosphonium compounds such as for example, n-butyltriphenylphosphonium bromide and methyltriphenyl phosphonium bromide.

Also, included herein are branched polycarbonates wherein apolyfunctional aromatic compound is reacted with the dihydric phenol andcarbonate precursor to provide a thermoplastic randomly branchedpolycarbonate.

These polyfunctional aromatic compounds contain at least threefunctional groups which are carboxyl, carboyxlic anhydride, haloformylor mixtures thereof. Examples of these polyfunctional aromatic compoundswhich may be employed in the practice of this invention include:trimellitic anhydride, trimellitic acid, trimellityl trichloride,4-chloroformyl phthalic anhydride, pyromellitic acid, pyromelliticdianhydride, mellitic acid, mellitic anhydride, trimesic acid,benzophenonetetracarboxylic acid, benzophenonetetracarboxylic anhydrideand the like. the preferred polyfunctional aromatic compounds aretrimellitic anhydride or trimellitic acid, or their haloformylderivatives.

Also, included herein are blends of a linear polycarbonate and abranched polycarbonate.

As indicated previously, the additive employed herein can consist ofmixtures of the metal salts. These mixtures can be mixtures of thevarious metal salts of the monomeric substituted aromatic sulfonic acidsor mixtures of the various metal salts of the polymeric substitutedaromatic sulfonic acids, or mixtures of the metal salts of the monomericand polymeric substituted aromatic sulfonic acids. The mixtures haveproven certain advantages such as V-O rating of 5 test bars andessentially zero number of drips per bar.

It iwll thus be seen that the objects set forth above among those madeapparent from the preceding description are efficiently attained andsince certain changes may be made in carrying out the above process andin the composition set forth without departing from the scope of thisinvention, it is intended that all matters contained in the abovedescription shall be interpreted as illustrative and not in a limitingsense.

What is claimed is:
 1. a non-opaque flame retardant aromatic carbonatepolymer composition comprising in admixture an aromatic carbonatepolymer and from 0.001 to about 2.0 parts per hundred part of thearomatic carbonate polymer of an additive selected from the groupconsisting of a metal salt of a monomeric substitued aromatic sulfonicacid and a polymeric substituted aromatic sulfonic acid and/ or mixturesthereof, and wherein said metal salts thereof are selected from thegroup consisting of the alkali metal salts and the alkali earth metalsalts, and mixtures thereof, and said substituent on the metal salts ofthe substituted aromatic sulfonic acid is selected from the groupconsisting of an electron withdrawing radical and mixtures thereof; saidaromatic carbonate polymer and additive having a refractive index in therange of 1.54 to 1.65.
 2. A shape article having a refractive index inthe range of 1.54 to 1.65 comprising in admixture an aromatic carbonatepolymer and from 0.001 to about 2.0 parts per hundred parts of thearomatic carbonate polymer of an additive selected from the groupconsisting of a metal salt of a monomeric substituted aromatic sulfonicacid and a polymeric substituted aromatic sulfonic acid and/or mixturesthereof, and wherein said metal salts thereof are selected from thegroup consisting of the alkali metal salts and the alkali earth metalsalts, and mixtures thereof, and said substituent on the metal salts ofthe substituted aromatic sulfonic acid is selected from the groupconsisting of an electron withdrawing radical and mixtures thereof. 3.The shaped article of claim 2 wherein the metal salt of the substitutedmonomeric aromatic sulfonic acid has the following formula:

    [A].sub.0-1 [R].sub.0-1 [B]

herein R is selected from the group of organic radicals consisting ofhalogen substituted and unsubstituted alkyl, aralkyl, alkaryl,aralkenyl, aryl, arylene, alkylidene, aralkylidene, alkenylidene andaralkenylidene radicals of 1-20 carbon atoms, and wherein A and B areindependently selected from the following formula:

    R'.sub.x (SO.sub.3 M).sub.y R"

wherein M is a metal selected from the group consisting of alkali metaland alkali earth metal, R' is an electron withdrawing radical, R" is anaryl radical of 1 to 4 aromatic rings, x is an integer of 0-17, y is aninteger of 0-10, provided that the sum of x must equal at least 1 andthe sum of y must equal at least 1 and whrein R is O and A is 1, the R"radicals of [A] and [B] are directly linked.
 4. The shaped article ofclaim 3 wherein the metal salt is:

    [R'.sub.x (SO.sub.3 M).sub.y R"] [R] [R'.sub.x (SO.sub.3 M).sub.y R"]

and the sum of x's equals 6 and the sum of y's equals
 4. 5. The shapedarticle of claim 3 wherein the metal salt is: ##STR4##
 6. The shapedarticle of claim 5 wherein M is sodium.
 7. The shaped article of claim 3wherein the metal salt is: ##STR5##
 8. The shaped article of claim 2wherein the metal salt of the substituted polymeric aromatic sulfonicacid has the following formula:

    [A].sub.m [R.sub.1 ].sub.m+n [B].sub.n

wherein R₁ is selected from the group of organic radicals consisting ofhalogen substituted and unsubstituted arylene, alkylene, aralkylene,alkenylene, aralkenylene, alkylidene, aralkylidene, alkenylidene andaralkenylidene radicals of 1-20 carbon atoms and wherein A and B areindependently selected from the following formula:

    R'.sub.x (SO.sub.3 M).sub.y R"

wherein M is a metal selected from the group consisting of alkali metaland alkali earth metal, R' is an electron withdrawing radical, R" is anaryl radical of 1-4 aromatic rings, x is an integer of 0-17, y is anineger of 0-10, provided that the sum of x must equal at least 1 and thesum of y must equal at least 1; and further wherein m is an integer offrom 0-2000 and n is an integer from 0-2000 provided, however, that thesum of m and n must equal at least
 4. 9. The shaped article of claim 2wherein the electron withdrawing radical is selected from the groupconsisting of halogen, nitro, trihalomethyl and cyano and mixturesthereof.
 10. The shaped article of claim 2 wherein the electronwithdrawing radical is a chlorine.
 11. The shaped article of claim 2wherein the electron withdrawing radical is trifluoromethyl.
 12. Theshaped article of claim 2 wherein the metal salt of the substitutedmonomeric aromatic sulfonic acid is the sodium salt of the sulfonic acidderived from ortho dichlorobenzene.
 13. The shaped article of claim 2wherein the metal salt of the substituted monomeric aromatic sulfonicacid is the sodium salt of pentachlorobenzenesulfonic acid.
 14. Theshaped article of claim 2 wherein the metal salt of the substitutedmonomeric aromatic sulfonic acid is the disodium salt of2,5-dichlorobenzene1,3-disulfonic acid.
 15. The shaped article of claim2 wherein the metal salt of the substituted polymeric aromatic sulfonicacid is the sodium salt of sulfonated poly(chlorostyrene).
 16. Theshaped article of claim 2 wherein the metal salt is sodiumtrichlorobiphenyl sulfonate.
 17. The shaped article of claim 2 whereinthe metal salt is sodium heptachlorobiphenyl sulfonate.
 18. The shapedarticle of claim 2 wherein the metal salt is sodium 1,1-bis(4-chlorophenyl)-2,2-dichloroethylene-3-sulfonate.
 19. The shapedarticle of claim 2 in the form of a sheet.
 20. The shaped article ofclaim 2 in the form of a particle.